Muravieva Viktoria K, Loginov Ivan P, Sukhikh Taisiya S, Ryzhikov Maxim R, Yanshole Vadim V, Nadolinny Vladimir A, Dorcet Vincent, Cordier Stéphane, Naumov Nikolay G
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences (SB RAS), 3 Acad. Lavrentiev ave., Novosibirsk 630090, Russia.
Novosibirsk State University; 2 Pirogova str., Novosibirsk 630090, Russia.
Inorg Chem. 2021 Jun 21;60(12):8838-8850. doi: 10.1021/acs.inorgchem.1c00763. Epub 2021 May 31.
The heterometallic cluster-based compound K[ReMoSe(CN)] was obtained by high-temperature reaction from a mixture of ReSe and MoSe in molten potassium cyanide. The redox behavior of the [ReMoSe(CN)] cluster anion was studied by cyclic voltammetry in aqueous and organic media showing two reversible one-electron-redox transitions with of -0.462 and 0.357 V versus Ag/AgCl in CHCN. Aqueous media potentials were found to be noticeably shifted to higher values because of solvation. Chemically accessible potentials allowed us to structurally isolate and characterize the [ReMoSe(CN)] ( = 3-, 4-, and 5-) cluster complex in several charge states with corresponding cluster skeletal electron (CSE) numbers ranging from 24 to 22. The electronic absorption of the [ReMoSe(CN)] cluster complex varies significantly upon a change of the CSE number, especially in the visible and near-IR regions. The local cluster core distortion upon electron removal was confirmed by density functional theory calculation, while the overall geometry of the cluster anion remained practically unaltered.
基于异金属簇的化合物K[ReMoSe(CN)]是通过在熔融氰化钾中使ReSe和MoSe的混合物进行高温反应而制得的。通过循环伏安法在水性和有机介质中研究了[ReMoSe(CN)]簇阴离子的氧化还原行为，结果表明在CHCN中相对于Ag/AgCl出现了两个可逆的单电子氧化还原转变，其电位分别为-0.462和0.357 V。由于溶剂化作用，发现水性介质中的电位明显向更高的值偏移。化学可及电位使我们能够在几种电荷状态下对[ReMoSe(CN)]（n = 3-、4-和5-）簇配合物进行结构分离和表征，相应的簇骨架电子（CSE）数范围为24至22。随着CSE数的变化，[ReMoSe(CN)]簇配合物的电子吸收有显著变化，尤其是在可见光和近红外区域。通过密度泛函理论计算证实了电子去除后簇局部核心的畸变，而簇阴离子的整体几何形状实际上保持不变。
